Anthraquinone dyestuffs



United States Patent 3,361,765 ANTHRAQUINONE DYESTUFFS Kurt Weber,Albert Riegler, and Otto Ruettner, Basel,

and Wiily- Mueller, Riehen, Switzerland, assignors to Ciba Limited,Basel, Switzerland, :1 Swiss company No Drawing. Filed Mar. 7, 1963,Ser. No. 263,423 Claims priority, application Switzerland, Mar. 13,1962,

2,998/62; Feb. 15, 1963, 1,901/63 6 Claims. (Cl. 260-3292) The presentinvention provides new water-insoluble dyestufis free from sulfonic acidgroups but containing at least one group of the formula which is boundeither directly or through an organic radical to one or several radicalsof the formula CONHF, in which formula F represents a radical of acolored organic compound and processes for their manufacture.

The new dyestuffs advantageously correspond to the formula in which Frepresents the radical of a colored organic compound, R represents adirect bond or the radical of an aliphatic, cycloaliphatic, aromatic orheterocyclic carboxylic acid, and n an integer of a value not greaterthan 5.

The new dyestus are obtainable as follows:

(a) a colored organic compound free from sulfonic acid groups andcontaining at least one acylatable amino group is reacted with a halideof a polycarboxylic acid in a ratio that ensures that the acylationproduct still contains at least one carboxylic acid halide group, andsaid acylation product is then reacted with ammonia, or

(b) a colored organic amine free from sulfonic acid groups is acylatedwith a halide of a carboxylic acid of the formula in which R has themeaning given above and m represents l or 2, or

(c) a dyestufi intermediate product that contains a radical of theformula 3 NHCO-R-CONH2 is converted into the finished dyestuff bysuitable reactions, for example, acylation, ring closure or coupling.

As starting materials for methods (a) and (b) there are advantageouslyused amino-anthraquinones, especially those that contain not more thanfused rings, preferably those of the formula I ll 1-amino-anthraquinone,

Lamina-3, -4, -5, -6, -7, or -8-chloranthraquinone, l-amino-4- or-5-methoxyanthraquinone, 1-arnino-4-, -5- or-8-benzoylaminoanthraquinone,

1-amino-6:7-dichloranthraquinone, Z-amino-anthraquinone,

1:4-, 1:5-, 1:6-, 1:7- or 1:8-diamino-anthraquinone, 5 -amino-1:9-isothiazoleanthrone,

4- or S-arnino-l :9-anthrapyrirnidine and 2 6- or 27-diamino-anthraquinone.

Further dyestulfs containing amino groups which can be used as startingmaterials for methods (a) and (b) of the process of the invention areamino-dioxazines, for example, those of the formulae nitro dyestufis,for example, those of the formulae or amino-azo dyestuffs, for example,those of the formulae COCH:

l NO: Cl

In method (a) the dyestuffs used as starting materials are condensedwith a halide of a polycarboxylic acid that is preferably aromatic, forexample, naphthalene-1:4-,

-1:5- or -2:6-dicarboxylic acid, fluoranthene-4z11-dicarboxylic acid,4:4'-diphenyl-dicarboxylic acid, 4:4'-azoaliphatic dicarboxylic acids,for example, oxalic acid.

At least one mole of the poly-carboxylic acid halide is used peracylatable amino group. Thus, for example, one mol of a diortricarboxylic acid chloride can be condensed with one mol of a coloredmonamine, and the one or two carboxylic acid chloride groups remainingin the resulting amide are converted into -CONH groups by reaction withammonia. It is also possible to condense a tricarboxylic acid chloridewith two mols of a colored monamine and to convert the carboxylic acidchloride group remaining in the resulting amide into a -CONH 7 group.

The reaction is advantageously carried out in an inert organic solvent,for example, nitrobenzene, orthodichlorobenzene or trichlorobenzene, ifnecessary, in the presence of an agent capable of binding acid, forexample, pyridine and its homologues, dimethylaniline or quinoline. Thereaction is advantageously performed at a raised temperature. It isadvantageous to use a large excess of polycarboxylic acid halide.

The further reaction of the intermediate product so obtained isadvantageously effected by means of ammonia either dissolved orsuspended in one of the aforementioned inert solvents, advantageously ata temperature above 100 C. and, if necessary, under superatmosphericpressure. Since the final product is insoluble in the solvent, even atan elevated temperature, it can be isolated by filtration.

In method (b) of the process of the invention, the aforesaid amines arecondensed with a halide of a carboxylic acid of the formula (2), inwhich R represents, for example, the radical of one of the diandpolycarboxylic acids of the kind defined. Thus, for example, thecarboxylic acid chloride of the formula HQNOCOCO 01 can be condensedwith a colored monamine in a molar can be condensed with a coloredmonamine in a molar ratio of 1:2.

These reactions are likewise advantageously carried out in an inertorganic solvent with the application of heat, in which process thedesired final products are obtained directly.

In method (c) of the process of the invention, a dyestuff intermediateproduct that contains the radical of the formula NHCO-R-C ONH f 2 B-COHN A HzNOC 4 is converted into the finished dyestufi by suitablereactions. This is efiected, for example, in such a manner that an amineof the formula HzN CONH:

in which the radical B and especially the radical A may containsubstituents, for example, halogen atoms, or alkoxy groups, is condensedwith a halide of a dyestuif carboxylic acid, for example, withazo-dyestufi carboxylic acid chlorides of the formulae N A i @0001,

(I10 CH3 1 u-N=N-on-o o-Nn@ o o 01 A1-N=N--[C-C ONH- B (IJOH OH;

in which formulae A represents radicals of diazo components, especiallythose of the benzene series, that are free from sulfonic groups, and thebenzene radicals B can contain further substituents that do not impartsolubility in water.

Furthermore, the diazo compound of an amine of the Formula 5 can becoupled with a coupling component that is free from sulfonic groups, forexample, with a B- hydroxynaphthoic acid arylide, a phenyl-pyrazolone oran acetic acid arylide.

An amine of the Formula 5 can also be used in the preparation of nitrodyestuffs, for example, the dyestuif of the formula CONH: OzN NH A NHC Ois obtained by condensation with 2:4-dinitrochlorobenzene.

Finally, an amine of the Formula 5 can be converted into a dyestufiintermediate product of the formula Oalk G1 OONH:

by reaction with chloranil in a molar ratio of 2:1, which product can beconverted into a dioxazine of the formula HzNOC by treating, accordingto known methods, with agents that cause ring closure, for example,benzoyl chloride or thionyl chloride. In the Formulae 6 and 7, the ringsA, in particular, can contain further substituents, for example, halogenatoms or alkoxy groups.

The new dyestuffs are valuable pigments that can be used for a very Widevariety of purposes, for example, they can be used in a finely dividedform for the spin dyeing of viscose rayon, cellulose ethers andcellulose esters, polyamides, polyurethanes and polyesters, and for thepreparation of colored lacquers or as lake formers. They may also beused for dyeing solutions and products made from cellulose acetate,nitro-cellulose, natural and synthetic resins such as polymerisationresins or condensation resins, for example, aminoplasts, alkyd resins,phenoplasts, poly-olefines such as polystyrene, polyvinylchloride,polyethylene, polypropylene, polyacrylonitrile and rubber, casein,silicones and silicone resins. They can also advantageously be used inthe manufacture of colored pencils, cosmetic preparations and laminatedsheets.

Those dyestufis obtained by the process of the invention that contain ananthraquinone radical as the color radical are also suitable for use asvat dyestuffs.

Unless otherwise stated, the parts and percentages in the followingexamples are by weight:

Example 1 8 parts of finely powdered l-amino-anthraquinone wereintroduced in small portions, while stirring well, into a mixture of 20parts of terephthaloyl chloride and 80 parts of dry nitrobenzene at 80C. The mixture was maintained at 95 to 100 C. until the amino compoundcould not be detected (about 2 hours). After cooling, the yellowcrystals were filtered off and freed from adherent acid chloride byWashing with dry nitrobenzene. 11 parts of the condensation product soprepared were stirred in 200 parts of dry nitrobenzene, and ammonia wasintroduced into the mixture at 100 to 110 C. in the course of 15 hours.The precipitated crystalline product was filtered hot, washedsuccessively with nitrobenzene, alcohol and water, and then dried. Thedyestutf so obtained of the formula 11111- OOCONH:

colored plasticized polyvinyl chloride yellow tints possessing a goodfastness to light and a very good fastness to migation. Compared withthe unsubstituted l-benzoylamino-anthraquinone, the dyestufi showed asubstantial improvement in respect of its fastness to migration.

By using 2:5-dibromoterephthaloyl chloride instead of terephthaloylchloride, a dyestuff having similar properties was obtained.

By using 1:3:5-benzene-tricarboxylic acid trichloride NHC o@ CONH:

instead of terephthaloyl chloride, a dyestufi was obtained of theformula (I) ONHg R WQ | CONHz I! that likewise colored polyvinylchloride yellow tints possessing very good properties of fastness.

Example 2 10 parts of the condensation product prepared as described inthe first paragraph of Example 1 from 1 mol ofl-amino-5-benzoylamino-anthraquinone and 1 mol of terephthaloyl chloridein nitrobenzene at C. were reacted with ammonia at 100 to C. in 200parts of nitrobenzene. The dyestuff so obtained of the formula unooQoomnOsman ti Example 3 12 parts of the condensation product prepared asdescribed in the first paragraph of Example 1 from one mol of1-amino-5-benzoylamino-anthraquinone and 1 mol of isophthaloyl chloridein nitrobenzene at 100 C. were reacted with ammonia at 100 to 110 C. in200 parts of nitrobenzene as described in Example 1. The dyestuff soobtained of the formula CIONHI colored plasticized polyvinyl chlorideyellow tints possessing good properties of fastness.

Dyeing prescription.(Vat dyeing on cotton). 4 parts of the dyestutfobtained in the manner described in the first paragraph were vatted at25 C. in 500 parts of water with 15 parts of sodium hydrosulfite in thepresence of 2.5 parts by volume of 10% sulfonated castor oil and 24parts by volume of 30% sodium hydroxide solution. The stock vat soobtained was added to 3000 parts of water. 100 parts of cotton were dyedfor 1 hour at 25 C. in the dyebath so prepared, and 480 parts of a 25%aqueous sodium chloride solution were added 15 minutes after thecommencement of dyeing. The cotton was then squeezed, oxidized in theair, acidified, rinsed, and then soaped at the boil. The cotton was dyeda strong yellow and the dyeing possessed very good properties offastness,

Example 4 15 parts of the condensation product prepared as described inthe first paragraph of Example 1 from 1 mol of1-amino-4-benzoylamino-anthraquinone and 1 mol of terephthaloyl chloridein nitrobenzene at 100 C. were reacted with ammonia at 100 to 100 C. in200 parts of nitrobenzene as described in Example 1. The dyestufi soobtained of the formula colored plasticized polyvinyl chloride ruby-redtints possessing very good properties of fastness and dyed cotton from avat bordeaux tints possessing very good properties of fastness.

By using 1-amino-4-para-chlorobenzoylamino-anthraquinone instead ofl-amino-4-benzoylamino-anthraqui none, a dyestuff possessing verysimilar properties was obtained.

Example 5 8 parts of finely powdered 1:5-diamino-anthraquinone wereintroduced in small portions, while stirring .well, into a mixture of 40parts of terephthaloyl chloride and 70 parts of dry nitrobenzene at 80C. The mixture was maintained at 100 to 105 C. until the amino-compoundcould no longer be detected (about 2 hours). After cooling, the yellowcrystals were filtered and freed from adherent acid chloride by washingwith dry nitrobenzene. 15 parts of the condensation product so preparedwere reacted with ammonia at 100 to 110 C. in 200 parts of nitrobenzeneas described in the second paragraph of Example 1. The dyestufi soobtained of the formula I nnooQ-corrm ll HzNOOQOOHN 0 coloredplasticized polyvinyl chloride yellow tints possessing a good fastnessto light and an excellent fastness to migration.

By using furanor thiophene-Z:S-dicarboxylic acid dichloride instead ofterephthaloyl chloride dyestufi's with similar properties were obtained.

Example 6 13 parts of the condensation product prepared as described inthe first paragraph of Example 5 from 1 mol of 1:5-diamino-anthraquinoneand 2 mols of isophthaloyl chloride were reacted with ammonia at 100 to110 C. in 200 parts of nitrobenzene as described in Example 1. Thedyestuff so obtained of the formula COHN O 1 0 ONE:

colored plasticized polyvinyl chloride yellow tints possessing a goodfastness to light and an excellent fastness to migration.

Example 7 15 parts of the condensation product prepared as described inthe first paragraph of Example 5 from 1 mol of l:4-diamino-anthraquinoneand 2 mols of terephthaloyl chloride were reacted with ammonia at 100 to110 C. in 200 parts of nitro-benzene as described in the secondparagraph of Example 1.

The dyestutf so obtained of the formula colored plasticized polyvinylchloride red tints possessing a good fastness to light and an excellentfastness to migration.

Example 8 10 parts of the condensation product prepared as described inExample 1 from 1 mol of 1-amino-4-hydroxyanthraquinone and 1 mol ofterephthaloyl chloride in nitrobenzene at 45 C. were reacted withammonia at to C. in 200 parts of nitrobenzene as described in Example 1.The dyestufi so obtained of the formula I 1 1110 OC -CONH2 II 00Hcolored plasticized polyvinyl chloride red tints possessing a very goodfastness to light and a good fastness to migration.

Example 9 No. Dyestufi formula Tint in polyvinyl chloride 9 I O1Blue-yiole't.

N o H 0 0 NHC o -o ONH:

(J OHN -o0 Ha I O N 2 I 0 ONE: :1 Do.

N 0 i i 1 01130 NHC oi j-o ONH; HNCOl JC OHN OCH 2 S O \N/ 3 11 (I31Claret. N 0 Q a NHC ONE: H NC 0- o OHN N 0 c1 NH0 0 -o ONHr HQNC 0 c OHN0/ \N/ or i or 1s Red. I

t 1TH NHC 0 -0 ONE:

E l 10 residue finally washed with hot water. The yield was 4.6

2.03 parts of terephthalic acid dichloride were dissolved in 150 partsof ortho-dichlorobenzene and to the solution were added in smallportions at to C., while stirring, 3.54 parts of the aminoazo dyestufiof the formula After a short time, the mono-condensation productcrystallized from the yellow solution. The mixture was stirred for 1hour at 40 to 45 C., then heated to 90 to 95 C. and 5 parts ofconcentrated ammonia added. The crystalline suspension of themono-condensation product was transformed into a thick, bright yellowmagma of the dicondensation product. After 15 minutes, the magma wassuction-filtered while hot, the filter residue washed with hotdichlorobenzene until the filtrate ran colorless, the

dichlorobenzene extracted with methanol, and the filter parts of adyestuft' of the formula 2.3 parts of terephthalic acid dichloride weredissolved in 200 parts of ortho-dichlorobenz ene and to the solutionwere added at room temperature, while stirring well, 5.5 parts of theamino-azo dyestuff of the formula OH H3 01 o ONE-GNHz 13 14 After ashort time, the mono-condensation product preylene and X is a memberselected from the group concipitated from the orange-red solution in theform of sisting of hydrogen, chlorine and -CONH red-orange crystals. Themixture was stirred for 2 hours 2. An anthraquinone dyestuif of theformula at 30 to 40 C., then heated to 90 to 95 C. and 2 parts ofconcentrated ammonia added. The mixture was trans- 5 O NHCO CONHZ formedinto a thick, light red magma of the di-condensation product. Afterstirring for 15 minutes, the magma was suction-filtered, and washed withhot dichlorobenzene until the filtrate ran colorless. Thedichlorobenzene was then extracted with cold methanol, and the residuefinally g I washed with hot water. The yield was 7 parts of a dye- NHCOstuff of the formula 01 in WhlCh X is a member selected from the groupconsisting of hydrogen, chlorine and CONH Q 3. The anthraquinonedyestuff of the formula 0 NHCO OH CH; 01 II I o ONHNHG 00-0 ONHQ CONH:

G1 which then worked into plastics such as polyvinyl chlol 1 ride, gaveyellowish red tints possessing a very good fastness to migration. 4. Theanthraquinone dyestuff of the formula Example 12 40.3 parts of themonoazo dyestuff prepared by cou- NHCO C TOONH pling diazotizedS-amino-Z:4-dich1orobenzoic acid with 2:3-hydroxynaphthoic acid wereheated for 2 hours at 115 to 120 C., while stirring, in admixture with500 parts of ortho-dichlorobenzene, 1 part of dimethyl-formamide and 24parts of thionyl chloride. After cooling the reaction mixture, thehomogeneous crystalline precipitate of the dicarboxylic acid chloride ofthe dyestutf was iso- 7 lated by filtration and then dried in vacuo at50 to 60 C. The anthraqumone d5 esmfi of the formula 1.78 parts of thedi-acid chloride so obtained were introduced into 120 parts ofortho-dichlorobenzene while I? NHCOOCONHZ stirring. A hot solution of2.8 parts of 1-amin0-2z5-dimethoxy-4(4-aminocarbonylbenzoylamino)-benzene in 200 parts ofortho-dichlorobenzene was then poured in 40 and the mixture heated for16 hours at 140 to 145 C. in I I I a bath. The pigment so formed wasfiltered hot, washed with hot ortho-dichlorobenzene, ethanol and water,and NZNOO OCONH 0 OK then dried. 3.95 parts (98.9% of the theoreticalyield) 6, The anthraquinone d t ff f the f l of a dark red powder wasobtained that was very sparing- HO OH ly soluble in organic solvents andyielded a red tint posg sessing a very good fastness to migration andlight when 0 NHCOG C worked into a polyvinyl chloride foil. I I

The dyestufi corresponded to the formula 0 NHCO C1 C1 l HC O H NOCI OCH:rmvooi': (Loch: ii

honnOmncoQ-oonm s N y References Cited l 0 011,

UNITED STATES PATENTS OH R 2,123,375 7/1938 Mieg et a1. 260-3772,713,059 7/1955 Gunthard 260372 CONHQNHCWQGONH 3,022,298 2/1962 Mory etal. 260246 CH3 3,065,229 11/1962 Ronco 260-246 3,078,281 2/1963 Braun eta1. 260-372 What is claimed is:

1. An anthraquinone dyestuft of the formula OTHER REFERENCESVenkataraman: Synthetic Dyes, vol. 2, pp. 786-91,

0 NHGORCONH, 891 (1952) (Academic Press). I 1 Modern PlasticsEncyclopedia, vol. 40 (Sept. 1962) pages 490 and 493.

Modern Plastics Encyclopedia, vol. 41 (Sept. 1963), page 402. {i IlIHQORX JAMES A. PATTEN, Primary Examiner.

in which R is a member selected from the group consist- RANDOLPHExaminer ing of meta-phenylene, para-phenylene and 2,5-thiophen- R. T.BOND, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No;3,361,765 January 2, 1968 Kurt Weber et a1.

It is certified that error appears in the above identified patent andthat said Letters Patent are hereby corrected as shown below: Cdlumn 14,lines 38 to 43, the left-hand portioh of the formula should appearas'shown-belowz N 'O- CONH Signed and. sealed this 25th day of November1969.

(SEAL) Attest:

EdWGId M- Fletcher, Jr. Attesting Offitr WILLIAM E. SCHUYLER, JR.

Commissioner of Patents

1. AN ANTHRAQUINONE DYESTUFF OF THE FORMULA
 6. THE ANTHRAQUINONEDYESTUFF OF THE FORMULA